JPH0788624B2 - Method for chemical modification of protein fiber - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for chemically modifying a protein fiber or a woven or knitted fabric thereof, more specifically,
Chemical modification for imparting light resistance to fibers or woven and knitted fabrics made of protein fibers such as silk, wool, animal hair fibers, and for improving practical performance such as wrinkle resistance, shrink resistance, and bulkiness Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Protein fibers such as silk, wool, other animal hair fibers, and feather fibers are generally expensive as compared with cellulosic fibers such as cotton and synthetic fibers, but are lightweight and strong. It is widely used as a high-quality woven or knitted fabric because it has excellent heat retention and has a unique texture and dignity.
Among them, silk fibers are especially high-quality woven and knitted fabrics because they have such characteristics as unique luster and silkiness and other unique elegance and dignity, and they are comfortable to wear and rich in design expression by dyeing. It is especially favored as

However, even protein-based fibers such as silk have the drawbacks of breaking, rubbing, and wrinkling, and also have the problem of yellowing due to ultraviolet rays, that is, poor light resistance. In the case of silk, the problem is more serious because it is particularly easy to yellow and is expensive, and in particular, significant improvement in light resistance is the most important issue. Moreover, although silk fabrics have been mainly used mainly in the field of Japanese garments in recent years, in recent years, they have made remarkable progress in the field of Western garments, and it is strongly hoped that the above problems will be urgently resolved by expanding such fields of use. It is rare.

Under these circumstances, various attempts have been made to improve the practical performance by subjecting protein fibers such as silk or fiber cloth to finishing treatment (chemical treatment) with various resin agents. Has been done. Among them, N-
Methylol acrylamide [N- (hydroxymethyl)
Acrylamide] or N-methylolmethacrylamide [N- (hydroxymethyl) methacrylamide] as a resin agent is immersed in a silk fiber (silk fiber cloth), and mainly wrinkle-proof, shrink-proof and bulky. Attention has been focused on a modified processing method for imparting such characteristics as described above.

When treating with such a resin agent, it is necessary to use an appropriate condensation catalyst for binding the resin agent to the fiber (condensation or graft polymerization), and various techniques depending on the type of condensation catalyst used. Proposed. When this kind of improvement processing is applied to cellulosic fibers such as cotton fabric, the technique of using an acid catalyst and a radical polymerization catalyst in combination as a condensation catalyst is almost established and put into practical use. When this method is applied to the protein fiber of
Since excessive polycondensation of methylol (meth) acrylamide amides causes problems such as the texture of the fiber cloth becoming too hard, a method using only an acidic catalyst has been studied.

However, since N-methylol (meth) acrylamide is a monomethyl compound, it has low reactivity and is not practical with a general acidic catalyst. In fact, a condensation reaction catalyst (eg, magnesium chloride, zinc nitrate, organic amine hydrochloride, etc.) that is commonly used for highly reactive dimethylol compounds, etc. has a significantly low effect of fixing the resin to the fiber (fiber cloth), and , In the case of protein fiber such as silk,
It becomes more difficult to obtain the resin processing effect because it is necessary to lower the curing temperature because it is more likely to be yellowed by heat as compared with the cellulose fiber.

In order to solve this, an aminoalkanecarboxylic acid (Japanese Patent Publication No. 63-30
75), tin compounds (Japanese Patent Publication No. 63-25110) or aluminum sulfate (Japanese Patent Publication No. 63-251).
No. 11), there is proposed an improved processing method for improving the practical properties of silk by resin processing with N- (hydroxymethyl) acrylamide or N- (hydroxymethyl) methacrylamide.

The reason why such a relatively strong acidic compound can be used as a condensation catalyst is that N- (hydroxymethyl) acrylamide and N- (hydroxymethyl) methacrylamide gelate in an acidic bath as compared with other resin agents. It is considered that it is difficult and that the protein fiber has the property of being more resistant to acid than the cellulose fiber.

However, in the method using the above-mentioned special condensation catalyst, although the effect of fixing the resin can be improved and the wrinkle resistance of silk can be improved to some extent, protein fibers such as silk and wool or fiber cloth, particularly There has been a serious problem that the low light resistance (yellowing due to ultraviolet rays), which is one of the major drawbacks of silk, cannot be sufficiently improved.

[0010]

The present invention has been made in view of the above problems. The present invention solves the above problems, and N- (hydroxymethyl) acrylamide,
N- (hydroxymethyl) methacrylamide, further N- (alkoxymethyl) acrylamide and N-
In the chemical processing of a fiber or a woven or knitted fabric composed of protein fibers such as silk with (alkoxymethyl) methacrylamide, while improving the properties such as wrinkle resistance, shrink resistance and bulkiness of the fiber or the woven or knitted fabric, It is an object of the present invention to provide a method for chemically modifying a protein-based fiber capable of sufficiently improving light resistance.

[0011]

As a result of intensive studies to solve the above-mentioned problems, the inventor of the present invention found that N-hydroxymethyl or N-alkoxymethyl was used as a fiber or woven or knitted fabric made of protein fibers such as silk. When the resin is processed with (meth) acrylamide, a method of immersing in a treatment liquid containing a specific compound such as amides and sulfamic acid, pre-drying, and then performing curing at a specific temperature or higher is the above-mentioned object. The present invention has been completed based on the finding that the method is a remarkably excellent method for practical use that sufficiently satisfies the above.

That is, the present invention provides a fiber or woven or knitted fabric made of a protein-based fiber with the following general formula: CH2 = CRCONHCH2 OX (1) [wherein, in the formula (1), R represents a hydrogen atom or a methyl group, X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] A method for chemically modifying a protein fiber, which comprises filling a treatment solution containing a compound represented by the formula [1] and sulfamic acid, preliminarily drying, and then performing curing at a temperature of 100 [deg.] C. or higher.

In the method of the present invention, the fibers made of the above-mentioned protein fibers used for chemical modification (resin processing) include silk fibers, wool fibers, other animal hair fibers, and feather fibers, or the like. Various fibers composed of two or more kinds of the above, and various mixed-spun fibers containing one or more of these as a main component can be mentioned, and among them, silk or one containing silk as a main component is preferably applied. .

The woven and knitted fabrics of the present invention include various fiber cloths and fiber products made of one or more of the above fibers, among which, among others,
A silk fiber cloth or a fiber cloth containing silk as a main component is preferably applied. As described above, in the present invention, either the fibers or the woven / knitted fabric (fiber cloth or the like) may be targeted, but normally, it is applied to the woven / knitted fabric (fiber product such as fiber cloth). Especially effective.

It is preferable that the fibers or fiber cloths such as silk to be used are scoured in advance before being treated with the treatment liquid. The scouring method is not particularly limited and may be carried out by various methods, but it is usually sufficient to carry out the scouring.

In the method of the present invention, it is important that the treatment liquid used for the fiber or woven or knitted material contains at least the compound represented by the general formula (1) and a specific compound called sulfamic acid. is there.

In the compound represented by the general formula (1) (hereinafter sometimes abbreviated as compound 1), R
May be either a hydrogen atom or a methyl group, and
X may be either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group and n-
Butyl group, isobutyl group (that is, 2-methylpropyl group), sec-butyl group (1-methylpropyl group) and tert-butyl group (1,1-dimethylethyl group)
Can be mentioned. Among these alkyl groups,
A methyl group and an ethyl group are particularly preferable. Further, a hydrogen atom is particularly preferable as X from the viewpoint of reactivity.

Specific examples of the compound 1 include N- (hydroxymethyl) acrylamide, N- (hydroxymethyl) methacrylamide, N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, and N- (ethoxy). Methyl) acrylamide, N- (ethoxymethyl) methacrylamide, N- (propoxymethyl) acrylamide, N- (propoxymethyl) methacrylamide, N- (isopropoxymethyl) acrylamide, N- (isopropoxymethyl) methacrylamide, N -(Butoxymethyl) acrylamide, N- (butoxymethyl) methacrylamide, N- (sec-butoxymethyl) acrylamide, N- (sec-butoxymethyl) methacrylamide, N- (isobutoxymethyl) acrylamide N- (iso-butoxymethyl) methacrylamide, N- (tert-butoxymethyl) can be mentioned acrylamide and N- (tert-butoxymethyl) methacrylamide.

Of these, N-hydroxymethyl acrylamide and N-hydroxymethyl methacrylamide are particularly preferable. In addition, these various compounds 1
May be used alone or in combination of two or more as required.

The sulfamic acid is a water-soluble acidic compound represented by NH 2 SO 3 H and also called amidosulfuric acid. As the sulfamic acid to be used, a pure one is particularly preferable, but a crude one may be used, and any of an anhydride, a hydrate and an aqueous solution can be used.
Generally, a commercially available product may be used as it is, but if necessary, it may be appropriately purified before use, or may be synthesized by a conventional method before use.

The treatment liquid is at least the compound 1
And an aqueous solution containing the sulfamic acid. The concentration of the compound 1 in the treatment liquid is not particularly limited and may be appropriately selected according to the type of fiber used, etc., but is usually preferably in the range of 80 to 200 g / l. Is.

If the concentration of the compound 1 in the treatment liquid is less than 80 g / l, the concentration is too low, and the amount of the resin adhered to the fiber becomes insufficient, so that the desired wrinkle resistance, shrink resistance and bulkiness are obtained. In some cases, improvement in practical performance such as is insufficient, or sufficient improvement in light resistance may not be obtained. On the other hand, the concentration is
If it exceeds 200 g / l, the concentration may be too high and the amount of resin fixed in the fiber may become excessive, and the texture of the fiber or woven or knitted fabric may be deteriorated.

The concentration of the sulfamic acid in the treatment liquid may be a relatively low concentration if it is used as a simple condensation reaction catalyst, for example, a concentration of 25 g / l or less is effective, but the main object of the present invention is In order to sufficiently achieve the improvement of the light resistance, it is usually 50 g / l or more,
It is recommended to select a concentration of 100 to 150 g / l.

If desired, the treatment liquid may appropriately contain other components than the compound 1, sulfamic acid, and water within a range not impairing the object of the present invention. Other components include various components such as those commonly used as components of conventional processing liquids of this type. Specifically, for example, radical polymerization catalysts such as potassium persulfate or peroxide, other condensation catalysts such as acid catalysts other than sulfamic acid, methacrylamide, other resin agents such as acrylamide, polymerization degree regulators, etc. However, the present invention is not limited to these. It should be noted that other condensation catalysts such as potassium peroxide should be added in a relatively low concentration range even when they are used.For example, when potassium peroxide is added, it is usually several It is desirable to select a concentration of about g / l or less. When other resin agents such as acrylamide and methacrylamide are added, it is recommended to add them so that the concentration in the treatment liquid is usually about 60 g / l or less.

In the method of the present invention, the fiber or woven or knitted material is saturated with the treatment liquid, preliminarily dried, and then cured at a temperature of 100 ° C. or higher. At that time, the saturate of the treatment liquid can be carried out by a conventional method, and usually it is carried out by immersing the fiber or the woven or knitted fabric in the treatment liquid and, if necessary, squeezing the liquid at an appropriate squeezing ratio. Be done. The temperature of the treatment bath (treatment liquid) at the time of performing this immersion is not particularly limited, but usually, it can be suitably performed at or near room temperature. The immersion time is not particularly limited as long as the fiber or the woven or knitted fabric is sufficiently wet with the treatment liquid, and generally may be several minutes to several tens of minutes, and usually several minutes.

The preliminary drying is usually preferably carried out in a state where the treatment liquid remains in a proportion of 60 to 120% with respect to the weight of the fiber or woven or knitted fabric containing the protein fiber. This ratio can be easily adjusted depending on the degree of squeezing liquid. This preliminary drying may be performed according to a conventional method, and for example, a method of air-drying at a temperature of room temperature to about 100 ° C. for about 200 to 2 minutes is suitably adopted.

A preferable range of the curing temperature is about 100 to 150 ° C. If the curing temperature is less than 100 ° C., the temperature is too low, and the desired processing effect due to condensation of the resin on the fiber or the effect of treatment with sulfamic acid is insufficient, and wrinkle resistance,
It is not possible to sufficiently achieve the objects of the present invention of improving practical performance such as shrink resistance and bulkiness and improving light resistance.
On the other hand, if the curing temperature is too high, the fibers or the woven or knitted fabric may be easily yellowed by heat. The curing time is usually 1 to 30 minutes, preferably 2 to 10 minutes. When the curing is completed as described above, post-treatments such as washing and drying (air-drying) for finishing are carried out according to a conventional method, if necessary.

By the chemical modification method of the present invention described in detail above, a fiber or woven or knitted fabric made of protein fiber such as silk,
In particular, it is possible not only to remarkably improve the practical properties such as wrinkle resistance, shrinkage resistance, and bulkiness, but also to impart sufficient light resistance, in particular, yellowing prevention performance against ultraviolet rays to silk.

[0029]

In the method of the present invention, as mentioned above, it is important to coexist (combine) with the known resin agent of Compound 1 a specific compound of sulfamic acid in the treatment liquid. By using this sulfamic acid together,
Not only can the practical performance such as wrinkle resistance, shrink resistance, and bulkiness be improved, but also the light resistance can be sufficiently improved.

The details of the mechanism of action of sulfamic acid are not clear at this stage, but the following points can be considered. First of all, sulfamic acid acts as a condensation catalyst that acts on the methyl group or alkoxymethyl group of the resin monomer (compound 1) during the curing to promote the condensation reaction on the fiber. it is conceivable that. Here, the effect only as a catalyst of this condensation reaction can be presumed to be sufficient even when the concentration of sulfamic acid in the treatment liquid is low as described above, and in fact, wrinkle resistance and shrinkage resistance even at low concentrations. It was confirmed that the practical performance such as the property and bulkiness was improved.

On the other hand, in order to impart sufficient light resistance, it is preferable that the concentration of sulfamic acid is relatively high as described above. This suggests that sulfamic acid has other important functions in addition to the function as a condensation catalyst. By the way, sulfamic acid is 10
Sulfamate group (-NHSO3 H) or sulfate group (-OSO3 H) that reacts with wool under high temperature above 0 ℃
It is known to give wool an excellent dye-proof property against anionic dyes such as acid dyes and direct dyes (Textile Research Journal, Volume 57, 619).
Pp. 1987). In view of these points, sulfamic acid not only promotes the condensation reaction of the resin agent (Compound 1) as the condensation catalyst, but also itself chemically binds to protein fiber such as silk, resulting in It is considered that the above-mentioned fibers or woven and knitted fabrics can have high light resistance.

Although it is not clear how this sulfamic acid chemically bonds to fibers other than wool such as silk, sulfamic acid chemically bonds to the active amino acid side chain of the protein fiber molecule, In the case of silk fiber, since the active amino group is contained only in a very small amount, it mainly reacts with the hydroxyl group of the side chain of tyrosine and serine to give sulf
It is considered that a light group is generated to improve light resistance. Thus, it is presumed that the treated fiber is significantly improved in light resistance as a result of the chemical blocking of the hydroxyl group of the tyrosine side chain, which is abundant in protein fibers, and stabilization. As a side effect of the introduction of the sulfone group, the treated fiber exhibits dye resistance to anionic dyes, but the dyeability with cationic dyes is significantly improved, and the dyeing fastness is also significantly improved. It was confirmed that things to do. further,
According to the method of the present invention, it is also confirmed that as a result of the intrafiber condensation reaction of the resin agent, wrinkle resistance, shrinkage resistance, and bulkiness are accompanied, and the type stability of the treated fiber is improved. It was

[0033]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Example 1) A Fuji silk fabric with 16 curses (silk spun fabric) having been refined was immersed in a treatment bath having the following composition for 5 minutes at room temperature, and then squeezed with a roll mangle at a squeezing ratio of 88%. did. Then pre-dry at 80 ° C for 3 minutes, then 12
Curing was performed at 5 ° C. for 5 minutes.

Composition of treatment bath (aqueous solution) -N- (hydroxymethyl) methacrylamide 120 g / l-Sulfamic acid 100 g / l

The processed silk samples thus obtained were sequentially subjected to a conventional method.
After washing with water and air drying, the performance of each fabric shown in Table 1 was evaluated. The evaluation results are shown in Table 1 together with the evaluation results of unprocessed silk which has not been subjected to the above-mentioned processing.

COMPARATIVE EXAMPLE 1 Example 1 was repeated except that the treatment bath used in Example 1 was replaced with a treatment bath having the following composition prepared according to the formulation described in JP-B-63-25111. A processed sample was prepared in the same manner and evaluated in the same manner. The results are shown in Table 1.

Composition of treatment bath (aqueous solution) -N- (hydroxymethyl) methacrylamide 120 g / l-Aluminum sulfate 100 g / l

[0039]

[Table 1]

(Example 2) A scoured silk double layer (with 10 swatches) was immersed in a treatment bath having the following composition for 5 minutes at room temperature, and then squeezed with a roll mangle to a squeezing rate of 90%. Then, it was pre-dried at 70 ° C. for 3 minutes and then cured at 125 ° C. for 5 minutes.

Composition of treatment bath (aqueous solution) N- (hydroxymethyl) acrylamide 100 g / l Sulfamic acid 80 g / l Potassium persulfate 1 g / l Methacrylamide 50 g / l

The obtained processed silk samples were sequentially subjected to a conventional method,
After washing with water and air-drying, the performance of each fabric shown in Table 2 was evaluated. The evaluation results are shown in Table 2 together with the evaluation results of unprocessed silk which has not been subjected to the above-mentioned treatment.

(Comparative Example 2) Example 2 was repeated except that the treatment bath used in Example 2 was replaced with a treatment bath having the following composition prepared according to the formulation described in JP-B-63-3075. Similarly, a processed sample was prepared and evaluated. The results are shown in Table 2.

-N- (hydroxymethyl) acrylamide 120 g / l-aminoacetic acid 15 g / l-magnesium chloride 5 g / l-potassium persulfate 1.2 g / l-methacrylamide 50 g / l

[0045]

[Table 2]

(Discussion) The results of Example 1 which is an example of the processing method of the present invention and the results of Comparative Example 1 which is an example of the conventional processing method are compared with reference to the case of unprocessed silk. Although the improvement of dry / wet wrinkle recovery is remarkably observed, the ability to prevent yellowing against ultraviolet irradiation is not observed at all in the silk processed by the conventional method (in the case of Comparative Example 1). On the other hand, the processed silk produced by the method of the present invention (in the case of Example 1) has an excellent ability to prevent yellowing, and the effect of sulfamic acid is clear.

The results of Example 2 which is another example of the processing method of the present invention and the results of Comparative Example 2 which is an example of the conventional processing method are compared with each other with reference to the case of unprocessed silk. Also in this case, the low wrinkle resistance and abrasion resistance, which are the drawbacks of silk, are remarkably improved, but the ability to prevent yellowing against ultraviolet irradiation is sufficiently achieved by the processed silk (Example 2) by the method of the present invention. On the other hand, it is clear that the silk processed by the conventional method (Comparative Example 2) is not recognized at all.

[0048]

According to the present invention, the treatment liquid (treatment bath) contains a specific resin agent (resin monomer), and
Since a specific compound called sulfamic acid coexists (combines) and is chemically processed at a temperature higher than a specific temperature, such as a specific resin processing, a fiber made of protein fiber or Practical use that not only imparts excellent wrinkle resistance, shrink resistance, bulkiness, and other practical performance to woven and knitted fabrics, especially silk, but also imparts high light resistance (preventing yellowing due to ultraviolet light, etc.) It is possible to provide a remarkably excellent method for chemically modifying a protein fiber.

Claims (1)

[Claims] 1. A protein-based fiber or a woven or knitted fabric thereof having the following general formula: CH2 = CRCONHCH2 OX (1) [In the formula (1), R represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or a carbon atom. It represents an alkyl group of the numbers 1 to 4. ] The chemical modification method of the protein fiber characterized by filling with the processing liquid containing the compound represented by these, and the sulfamic acid, pre-drying, and then performing curing at a temperature of 100 ° C. or higher.